Flavoring with dialkylthioalkenes, dialkylthioalkylcycloalkenes and monoalkylthioalkenylcycloalkenes

ABSTRACT

Described are dialkylthioalkenes, dialkylthioalkylcycloalkenes and monoalkylthioalkenylcycloalkenes defined according to the generic structure: ##STR1## as well as the genus defined according to the structure: ##STR2## wherein R represents C 6  -C 11  alkenyl or cycloalkenylalkyl; and wherein R 2  represents C 1  -C 3  alkyl and R 3  is C 1  -C 3  alkyl and organoleptic uses thereof in augmenting or enhancing the aroma or taste of foodstuffs, chewing gums, toothpastes or medicinal products.

This is a divisional of application Ser. No. 731,919, filed May 8, 1985,now U.S. Pat. No. 4,565,707.

BACKGROUND OF THE INVENTION

This invention describes dialkylthioalkenes,dialkylthioalkylcycloalkenes and monoalkylthioalkenylcycloalkenesdefined according to the generic structure: ##STR3## wherein Rrepresents C₆ -C₁₁ alkenyl or cycloalkenylalkyl; and R₂ represents C₁-C₃ alkyl and uses thereof in augmenting or enhancing the aroma or tasteof foodstuffs, chewing gums, toothpastes and medicinal products.

Artificial flavoring agents for foodstuffs have received increasingattention in recent years. In many areas such food flavoring agents arepreferred over natural flavoring agents at least in part because of theuniform flavor that may be so obtained. For example, natural foodflavoring agents such as extracts, essences, concentrates and the likeare often subject to wide variation due to changes in the quality, typeand treatment of the raw materials. Such variation can be reflected inthe end product and results in unreliable flavor characteristics anduncertainty as to consumer acceptance and cost. Additionally, thepresence of the natural product in the ultimate food may be undesirablebecause of the increased tendency to spoil. This is particularlytroublesome in convenience and snack food usage where such products asdips, soups, chips, prepared dinners, canned foods, sauces, gravies andthe like are apt to be stored by the consumer for some time prior touse.

The fundamental problem in preparing artifical flavoring agents is thatof achieving as nearly as possible a true flavor reproduction. Thisgenerally proves to be a difficult task since the mechanism forflavoring development in many foods is not understood. This is notablein products having blueberry, blackcurrant, guava, grapefruit, tomato,garlic and hydrolyzed vegetable protein-like taste nuances.

Reproduction of blueberry, blackcurrant, vanilla, guava, grapefruit,galbanum, tomato, garlic, green, hydrolyzed vegetable protein-like,beany and cooked vegetable-like, fried onion, floral, roasted, onion,crisp roasted, bacon, sweet, cherry and marachino cherry-like aroma andtaste naunces has been the subject of a long and continuous search bythose engaged in the production of foodstuffs, chewing gums, toothpastesand medicinal products. The severe shortage of foods, especially proteinfoods, in many parts of the world has given rise to the need forutilizing non-met sources of proteins and making such protein aspalatable and as meat-like as possible. Hence, materials which willclosely simulate or exactly reproduce the flavor or aroma of mushroom,hydrolyzed, vegetable protein and garlic are required. Furthermore, meatflavors have been enhanced previously by the use of such materials asmonosodium glutamate. In many diets monosodium is not desired.Therefore, a need has arisen for a monosodium glutamate replacer.

Moreover, there are a great many of meat cotaining or meat based foodspresently distributed in a preserved form. Examples of such substancesare condensed soups, dry-soup mixes, dry meat, freeze-dried orlyophilized meats, packaged gravies and the like. While these productscontain meat or meat extracts, the fragrance, taste and otherorganoleptic factors are very often impaired by the processing operationand it is desirable to supplement or enhance the flavors of thesepreserved foods with versatile materials which have hydrolyzed vegetableprotein-like nuances as well as garlic and beany nuances.

U.S. Pat. No. 4,472,446 issued on Sept. 18, 1984 disclosesmethyl(methylthioalkyl)-1,3-dithiolanes defined according to thestructure: ##STR4## wherein R₁ and R₂ are the same or different and eachrepresents methyl or hydrogen with the proviso that at least one of R₁and R₂ is methyl; and wherein m represents an interger of 1 or 2 as wellas methods for augmenting or enhancing or modifying the organolepticproperties, e.g., taste and aroma of said foodstuffs. Themethyl(methylthioalkyl)-1,3-dithiolanes of U.S. Pat. No. 4,472,446 areindicated therein to augment or enhance meat, turkey, hydrolyzedvegetable protein, mushroom, bread-like, meat extract, beef broth, potroast, onion and brothy flavored foodstuffs.

The methyl(methylthioalkyl)-1-3-dithiolanes of U.S. Pat. No. 4,472,446are indicated therein to provide meaty, hydrolyzed vegetableprotein-like, sweet, meat extract-like, mushroom-like, turkey-like,chicken-like, port-like and butterscotch-like aroma nuances and oniony,onion/roasted hydrolyzed vegetable protein-like, sweet, meaty, meatextract-like, bready, mushroom-like, turkey-like, chicken-like,pork-like and butterscotch-like taste nuances.

Nothing in the prior art discloses the dialkylthioalkenes,dialkylthioalkylcycloalkenes and monoalkylthioalkeneylcycloalkenes ofour invention are uses thereof in augmenting or enhancing the aroma ortaste of foodstuffs, chewing gums, toothpastes and medicinal products.The dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkeneylcycloalkenes of our invention and organoleptic usesthereof are unobvious, unexpected and advantageous with respect to otheracetals or ketals of the prior art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the compound having the structure:##STR5## prepared according to Example I (Conditions: Field strength:100 MHz; Solvent: CFCl₃).

FIG. 2 is the NMR spectrum for the mixture produced according to ExampleII(A) of compounds having the structures: ##STR6## with the mole ratioof the compound having the structures: ##STR7## being approximately 8:2(Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 3 is the NMR spectrum of the mixture of compounds having thestructures: ##STR8## prepared according to Example II(B) with the moleratio of the compound having the structure: ##STR9## to the compoundhaving the structure: ##STR10## being approximately 65:30 (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 4 is the NMR spectrum for the mixture of compounds having thestructures: ##STR11## prepared according to Example III. The mole ratioof the compound having the structure: ##STR12## to the compound havingthe structure: ##STR13## is approximately 65:35. (Conditions: Fieldstrength: 100 MHz; Solvent: CFCl₃).

FIG. 5 is the NMR spectrum for the mixture of compounds having thestructures: ##STR14## produced according to Example III. (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 6 is the NMR spectrum for the compound having the structure:##STR15## produced according to Example III. (Conditions: Fieldstrength: 100 MHz; Solvent: CFCl₃).

FIG. 7 is the NMR spectrum for the compound having the structure:##STR16## prepared according to Example IV (Conditions: Field strength:100 MHz; Solvent: CFCl₃).

FIG. 8 is the GLC profile for the crude reaction product of Example XVIcontaining the compounds having the structures: ##STR17## (Conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute.

FIG. 9 is the NMR spectrum for the compound having the structure:##STR18## of the peak indicated by reference numeral 81 of the GLCprofile of FIG. 8, produced according to Example XVI (Conditions: Fieldstrength: 100 MHz; Solvent: CFCl₃).

FIG. 10 is the NMR spectrum for the compound having the structure:##STR19## of the peak indicated by reference numeral 82 of FIG. 8,produced according to Example XVI (Conditions: Field strength: 100 MHz;Solvent: CFCl₃).

FIG. 11 is the GLC profile for the crude reaction product producedaccording to Example XVII containing the compounds having thestructures: ##STR20## (Conditions: Carbowax column programmed at 220° C.isothermal).

FIG. 12 is the NMR spectrum for the peak indicated by reference numeral111 of FIG. 11, for the compound having the structure: ##STR21##(Conditions: Field strength: 100 MHz; Solvent: CFCl₃).100.

FIG. 13 is the NMR spectrum for the compound having the structure:##STR22## produced according to Example XVII, of the peak indicated byreference numeral 112 of FIG. 11. (Conditions: Field strength: 100 MHz;Solvent: CFCl₃).

FIG. 14 is the GLC profile for the crude reaction product of Example XXIcontaining the compounds having the structures: ##STR23##

FIG. 15 is the GLC profile for Fraction 5 of the distillation of thereaction product of Example XXI containing 80% by weight of the compoundhaving the structure: ##STR24##

FIG. 16 is the NMR spectrum for Fraction 5 of the distillation of thereaction product of Example XXI containing the compound having thestructure: ##STR25## (Conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 17 is the NMR spectrum for purified Fraction 5 of the distillationof the reaction product of Example XXI containing 85% by weight of thecompound having the structure: ##STR26## ("Z":"E" ratio=2:1).

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 8 is the GLC profile for the crude reaction product of Example XVIIcontaining the compounds having the structures: ##STR27## (Conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute).

The peak indicated by reference numeral 81 is the peak for the compoundhaving the structure: ##STR28## The peak indicated by reference numeral82 is the peak for the compound having the structure: ##STR29##

FIG. 11 is the GLC profile for the crude reaction product of ExampleXVII containing the compounds having the structures: ##STR30##(Conditions: (Carbowax column programmed at 220° C. isothermal).

The peak indicated by reference numeral 111 is the peak for the compoundhaving the structure: ##STR31## The peak indicated by reference numeral112 is the peak for the compound having the structure: ##STR32##

FIG. 14 is the GLC profile for the crude reaction product of Example XXIcontaining the compounds having the structures: ##STR33## (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute). The peakindicated by reference numeral 140 is the peak for the reaction solvent,methylene chloride. The peak indicated by reference numeral 141 is thepeak for the starting material, β-homocyclocitral having the structure:##STR34## The peak indicated by reference numeral 142 is the peak forthe compound having the structure: ##STR35## The peak indicated byreference numeral 143 is the peak for the compound having the structure:##STR36##

FIG. 15 is the GLC profile for Fraction 5 of the distillation of thereaction product of Example XXI containing the compound having thestructure: ##STR37## (Conditions: 8'×0.125" SE-30 column programmed at100°-220° C. at 8° C. per minute). The peak indicated by referencenumeral 150 is the peak for the compound having the structure: ##STR38##

INVENTION

The present invention provides the novel dialkylthioalkenes,dialkylthioalkylcycloalkenes and monoalkylthioalkeneylcycloalkenesuseful for augmenting or enhancing the aroma or taste of foodstuffs,chewing gums, toothpastes and medicinal products, saiddialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkeneylcycloalkenes being defined according to the genericstructure: ##STR39## wherein R represents C₆ -C₁₁ alkenyl orcycloalkenylalkyl aand R₂ represents C₁ -C₃ alkyl as well as methods foraugmenting or enhancing or modifying the organoleptic properties, e.g.,taste and aroma of said foodstuffs, chewing gums, medicinal products andtoothpastes. The genus defined according to the structure: ##STR40##also includes the subgenus having the structure: ##STR41## wherein R₂represents C₁ -C₃ alkyl and R₁ represents C₅ -C₁₀ alkenyl orcycloalkenylalkyl.

The dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkeneylcycloalkenes of our invention augment or enhanceblueberry, raspberry, blackcurrant, guava, tropical fruit, garlic,hydrolyzed vegetable portein and cooked bean flavored foodstuffs,chewing gums, toothpastes, and medicinal products. Thedialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkeneylcycloalkenes of our invention provide blueberry,blackcurrant, vanilla, guava, grapefruit, galbanum-like, tomato,sulfury, garlic, green, hydrolyzed vegetable protein-like, beany andcooked vegetable fried onion, floral, roasted, onion, crisp roasted,bacon, sweet, cherry and marachino cherry-like aroma and taste nuances.

The dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkeneylcycloalkenes of our invention defined according tothe generic structure: ##STR42## wherein R represents C₆ -C₁₁ alkenyl orcycloalkenyl alkyl and R₂ represents C₁ -C₃ alkyl may be produced bymeans of reacting an alkyl mercaptan having the structure:

    R.sub.2 --SH

with an aldehyde having the structure: ##STR43## wherein R₁ representsC₅ -C₁₀ alkenyl or cycloalkenylalkyl and R₂ represents C₁ -C₃ alkyl inthe presence of a protonic acid catalyst such as paratoluene sulfonicacid, xythene sulfonic acid, methan sulfonic acid, phosphoric acid andconcentrated sulfuric acid.

The reaction may be illustrated thusly: ##STR44##

The reacton temperature may vary from about 0° C. up to about 25° C.with a preferred reaction temperature range of 0°-10° C. The reactiontime may vary from about 5 hours up to about 20 hours. The reactiontakes place by bubbling in the alkyl mercaptan having the structure:

    R.sub.2 --SH

into the reaction mass which contains in addition to reactant aldehydehaving the structure: ##STR45## a suitable solvent. The solvent for thereaction is one that is inert to both the products and the reactants andis also one that may easily be recovered from the reaction mass as bycomplete removal on distillation, in view of the fact that the reactionmass as by complete removal on distillation, in view of the fact thatthe reaction products are used as food flavors, medicinal productflavors, chewing gum flavors and toothpaste flavors for internalconsumption. Accordingly, suitable solvents are cyclohexane,cyclopentane, cyclooctane, 1-methylcyclohexane, 1,2-dimethylcyclohexane,1,2,4-trimethylcyclohexane, methylene chloride (CH₂ --Cl₂),2-ethyltetrahydrofuran, 2,5-dimethyltetrahydrofuran and the like.

Examples of the products of our invention and their organolepticproperties are as follows:

                  TABLE I                                                         ______________________________________                                                        Organoleptic Properties                                       ______________________________________                                         ##STR46##        A blueberry, blackcurrant and vanilla aroma and taste                         profile at 3 ppm causing it to be useful in blueberry,                        raspberry and blackcurrant flavored foodstuffs.             prepared according                                                            to Example I.                                                                  ##STR47##        A guava, grapefruit, galbanum, tomato and sulfury aroma                       and taste profile at 0.2 ppm causing it to be useful in                       uava and tropical fruit flavored foodstuffs.                prepared according                                                            to Example II(A) (mole                                                        ratio of compound                                                             having the structure:                                                          ##STR48##                                                                    to compound having structure:                                                  ##STR49##                                                                     ##STR50##        A garlic and green aroma and taste profile at 1 ppm                           causing it to be useful in garlic and onion flavored                          foodstuffs.                                                 prepared according                                                            to Example III (ratio                                                         of compound having                                                            the structure:                                                                 ##STR51##                                                                    and                                                                            ##STR52##                                                                     ##STR53##        A hydrolyzed vegetable protein-like, beany, cooked                            vegetable aroma and taste profile at 0.01 ppm causing                         it to be useful in hydrolyzed vegetable protein, meaty                        and cooked bean flavored foodstuffs.                         ##STR54##        A garlic and fried onion aroma and taste profile at 20                        ppm causing it to be useful in onion soups and garlic                         flavored foodstuffs.                                         ##STR55##        A floral, green and roasted aroma and taste profile at                        0.5 ppm causing it to be useful in almond, roasted                            peanut and baked goods flavored foodstuffs.                  ##STR56##        An oniony, roasted, crisp roasted bacon aroma and taste                       profile at 2 ppm causing it to be useful in bacon,                            roasted nut, roasted onion, almond and peanut flavored                        foodstuffs.                                                  ##STR57##        A sweet, cherry, marachino, cherry, oniony and bacon                          aroma and taste profile at 0.1 ppm causing it to be                           useful in cherry and black cherry flavored                  ______________________________________                                                          foodstuffs.                                             

At the end of the reaction as stated, supra, the reaction product isextracted from the reaction mass or the reaction mass is washed, forexample, with saturated sodium chloride. The reaction product is thendistilled preferably by means of vacuum distillation.

Thus, dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes produced according to our invention canbe used to alter, vary fortify, modify, enhance or otherwise improve theorganoleptic properties, including flavor and/or aroma, of a widevariety of materials which are ingested, consumed, or otherwiseorganoleptically sensed.

The term "alter" in its various forms will be understood herein to meanthe supplying or imparting a flavor character or note to an otherwisebland, relatively tasteless substance, or augmenting an existing flavorcharacteristic where the natural flavor is deficient in some regard, orsupplementing the existing flavor or aroma impression to modify theorganoleptic character. The materials which are so altered are generallyreferred to herein as consumable materials.

Such dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes of our invention are accordingly usefulin flavoring compositions. Flavoring compositions are hereintaken tomean those which contribute a part of the overall flavor impression bysupplementing or fortifying a natural or artificial flavor in amaterial, as well as those which supply substantially all the flavorand/or aroma character to a consumable article.

The term "foodstuff" as used herein includes both solid and liquidingestible materials for man or animals, which materials usually do, butneed not, have nutritional value. Thus, foodstuffs includes meats,gravies, soups, convenience foods, malt and other alcoholic ornon-alcoholic beverages, milk and dairy products, nut butters such aspeanut butter and other spreads, seafoods including fish, crustaceans,mollusks and the like, candies, breakfast foods, baked goods,vegetables, cereals, soft drinks, snack foods, dog and cat foods, otherveterinary products, and the like.

When the dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes according to this invention are used ina food flavoring composition, they can be combined with conventionalflavoring materials or adjuvants. Such co-ingredients or flavoringadjuvants are well known in the art for such use and have beenextensively described in the literature. Apart from the requirement thatany such adjuvant material is ingestibly acceptable, and thus non-toxicor otherwise non-deleterious, conventional materials can be used andbroadly include other flavor materials, vehicles, stabilizers,thickeners, surface active agents, conditioners and flavor intesifiers.

Examples of preferred co-flavoring adjuvants are:

Methyl thiazole alcohol (4-methyl-5-beta-hydroxyethyl thiazole);

2-Methyl butanethiol;

4-Mercapto-2-butanone;

3-Mercapto-2-pentanone;

1-Mercapto-2-propanone;

Benzaldehyde;

Furfural;

Furfuryl alcohol;

2-Mercapto propionic acid;

Alkyl pyrazine;

Methyl pyrazine;

2-Ethyl-3-methyl pyrazine;

Tetramethyl pyrazine;

Polysulfides;

Dipropyl disulfide;

Methyl benzyl disulfide;

Alkyl thiophenes;

2-Butyl thiophene;

2,3-Dimethyl thiophene;

5-Methyl furfural;

Acetyl furan;

2,4-Decadienal;

Guiacol;

Phenyl acetaldehyde;

β-Decalactone;

d-Limonene;

Acetoin;

Amyl acetate;

Maltol;

Ethyl butyrate;

Luvulinic acid;

Piperonal;

Ethyl acetate;

n-Octanal;

n-Pentanal;

n-Hexanal;

Diacetyl;

Monosodium glutamate;

Monopotassium glutamate;

Sulfur-containing amino acids, e.g., Cysteine;

Hydrolyzed vegetable protein;

2-Methylfuran-3-thiol;

2-Methyldihydrofuran-3-thiol;

2,5-dimethylfuran-3-thiol;

Hydrolyzed fish protein;

Tetramethyl pyrazine;

Propylpropenyl disulfide;

Propylpropenyl trisulfide;

Diallyl disulfide;

Diallyl trisulfide;

Dipropenyl disulfide;

Dipropenyl trisulfide;

4-Methyl-2-[methylthio)-ethyl]-1,3-dithiolane;

4,5-Dimethyl-2[methylthio)ethyl]-1,3-dithiolane;

4,5-Dimethyl-2-(methylthiomethyl)-1,3-dithiolane;

4-Methyl-2-(methylthiomethyl)-1,3-dithiolane.

The dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes or the compositions incorporating them,as mentioned above, can be combined with one or more vehicles orcarriers for adding them to the particular product. Vehicles can beedible or otherwise suitable materials such as ethyl alcohol, propyleneglycol, water and the like. Carriers include materials such as gumarabic, carrageenan, other gums and the like.

The dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes according to this invention can beincorporated with the carriers by conventional meams such asspray-drying, drum-drying and the like. Such carriers can also includematerials for coacervating the dialkylthioalkenes,dialkylthioalkylcycloalkenes and monoalkylthioalkenylcycloalkenes (andother flavoring ingredients, as present) to provide encapsulatedproducts. When the carrier is an emulsion the flavoring composition canalso contain emulsifiers such as mono- and diglycerides or fatty acidsand the like. With these carriers or vehicles, the desired physical formof the composition can be prepared.

The quantity of dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes utilized should be sufficient to impartthe desired flavor characteristic to the product, but on the other hand,the use of an excessive amount of the derivative is not only wastefuland uneconomical, but in some instances too large a quantity mayunbalance the flavor or other organoleptic properties of the productconsumed. The quantity used will vary depending upon the ultimatefoodstuff; the amount and type of flavor

Initially present in the foodstuff; the further process or treatmentsteps to which the foodstuff will be subjected; regional and otherpreference factors; the type of storage; if any, to which the productwill be subject; and the preconsumption treatment, such as baking,frying, and so on, given to the product by the ultimate consumer.Accordingly, the terminology "effect amount" and "sufficient amount" isunderstood in the context of the present invention to be quantitativelyadequate to alter the flavor of the foodstuff.

It is accordingly preferred that the ultimate composition containingfrom about 0.001 parts per million (ppm) to about 250 ppm ofdialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes or mixtures thereof. More particularly,in food compositions it is desirable to use from about 0.001 ppm to 100ppm for enhancing flavors and in certain preferred embodiments of theinvention, from about 0.001 to 50 ppm of the derivatives are included toadd positive flavors to the finished product.

The dialkylthioalkenes, dialkylthioalkylcycloalkenes andmonoalkylthioalkenylcycloalkenes or mixtures thereof of our invention tobe utilized in flavoring compositions can be varied over a wide rangedepending upon the particular quality to be added to the foodstuff.Thus, amounts of one or more derivatives according to the presentinvention of from about 0.05 ppm up to 80 or 90 percent of the totalflavoring composition can be incorporated in such compositions. It isgenerally found to be desirable to include from about 0.05 ppm up toabout 0.1 percent of the dialkylthioalkenes,dialkylthioalkylcycloalkenes and monoalkylthioalkenylcycloalkenes insuch compositions.

The following examples are given to illustrate embodiment of theinvention as it is preferred to practice it. It will be understood thatthese examples are illustrative and the invention is not to beconsidered as restrictive thereto except as indicated in the appendedclaims.

All parts, proportions, percentages, and ratios here are by weightunless otherwise indicated.

EXAMPLE I PREPARATION OF2-[2,2-BIS(METHYLTHIO)ETHYL]-1,3-TRIMETHYLCYCLOHEXENE

Reaction: ##STR58##

Into a 500 cc reaction flask equipped with stirrer, thermometer, refluxcondenser, heating mantle and gas bubbler are placed 200 ml cyclohexane;0.5 grams paratoluene sulfonic acid and 25 grams of homocyclocitralhaving the structure: ##STR59##

The resulting mixture is then stirred and cooled using anisopropylalcohol ice bath down to 0° C. Over a period of 8 hours withstirring while maintaining the reaction temperature at 0° C., 25 gramsof methyl mercaptan is bubbled into the reaction mass. At the end of theaddition of the methyl mercaptan, the reaction mass is stirred for aperiod of 8 hours at 0° C. At the end of this period, the reaction massis washed with 3 volumes of saturated sodium chloride solution followedby 10 percent sodium bicarbonate solution. 10 percent sodium bicarbonatesolution. The reaction mass is then fractionally distilled yielding theproduct having the structure: ##STR60##

This product has an excellent blueberry, blackcurrant and vanilla aromaand taste profile at 3 ppm causing it to be useful in blueberry,raspberry and blackcurrant flavored foodstuffs, e.g., blackberryflavored beverages, raspberry flavored gelatin deserts and blackcurrantpreserves (e.g., blackcurrant "jam".

FIG. 1 is the GLC profile of the compound having the structure:##STR61## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE II(A) PREPARATION OF MIXTURE OF 1,1-BIS(METHYLTHIO)-E-2-HEXENEAND 1,3-BIS(METHYLTHIO)-E-1-HEXENE

Reaction: ##STR62##

Into a 500 cc reaction flask equipped with stirrer, thermometer,isopropylalcohol cooling bath, reflux condenser and gas bubbler areplaced 200 ml cyclohexane; 25 grams of E-2-hexenal and 0.5 grams ofparatoluene sulfonic acid. Using the isopropylalcohol/ice cooling baththe reaction mass is cooled to 0° C. Over a period of 12 hours, 50 gramsof methyl mercaptan is bubbled into the reaction mass with stirring. Thereaction mass is then maintained at 0° C. for a period of 8 hours withstirring. The reaction mass is then washed with 3 volumes of saturatedaqueous chloride solution followed by 3 volumes of 10 percent sodiumbicarbonate. The reaction mass is then fractionally distilled yielding amixture of compounds having the structures: ##STR63## with the moleratio of the compound having the structure: ##STR64## to the compoundhaving the structure: ##STR65## being 8:2. The resulting product has anexcellent guava, grapefruit, galbanum, tomato and sulfury aroma andtaste profile at 0.2 ppm.

FIG. 2 is the NMR spectrum for the resulting mixture of compounds havingthe structure: ##STR66## (Conditions: Field strength: 100 MHz; Solvent:CFCl₃).

EXAMPLE II(B)

Another reaction is run using the above conditions except that 200 mlmethylene chloride is used instead of 200 ml cyclohexane. In addition,the reaction is run at 10° C. instead of 0° C.

The resulting product is a mixture of compounds having the structures:##STR67## with the mole ratio of the compound having the structure:##STR68## to the compound having the structure: ##STR69## being 65:30.

FIG. 3 is the NMR spectrum for the resulting mixture. (Conditions: Fieldstrength: 100 MHz; Solvent: CFCl₃).

The resulting mixture has an excellent guava, grapefruit, galbanum,tomato and sulfury aroma and taste profile at 0.2 ppm causing it to beuseful in guava and tropical fruit flavored foodstuffs, for example,guava nectar and tropical fruit flavored juices.

EXAMPLE III PREPARATION OF MIXTURE OF 1,1-BIS(METHYLTHIO)-Z-3-HEXENE;1,3-BIS(METHYLTHIO)-E-1-HEXENE AND1-[(3-HEXENYL)OXY]-1-(METHYLTHIO)-Z-Z-3-HEXENE

Reaction: ##STR70##

Into a 500 cc reaction flask equipped with stirrer, thermometer, refluxcondenser and gas bubbler is placed 200 ml methylene dichloride (CH₂ Cl₂; 0.5 grams of paratoluene sulphonic acid and 27 grams of cis-3-hexenal.The reaction mass is cooled to 0° C. with an isopropional ice bath. Withstirring over a period of 8 hours, 10 grams of methyl mercaptan isbubbled into the reaction mass. At the end of the 8 hour period, thereaction mass is washed with 3 volumes of saturated aqueous sodiumchloride followed by 3 volumes of 10 percent aqueous sodium bicarbonatesolution. The reaction mass is then dried over anhydrous sodium sulfate,stripped of solvent and fractionally distilled yielding a mixture of thecompounds having the structures: ##STR71##

The compound having the structure: ##STR72## is separated from themixture of compounds having the structures: ##STR73##

The mixture of compounds having the structures: ##STR74## is a moleratio of 65:35 of the compound having the structure: ##STR75## to thecompound having the structure: ##STR76##

A resulting 65:35 mixture of compounds having the structures: ##STR77##as an intense, fresh garlic, green aroma profile with a garlic, greenand sulfury taste as 1 ppm causing it to be useful in garlic and onionflavored foodstuffs.

FIG. 4 is the NMR spectrum for the mixture of compounds having thestructures: ##STR78## with the mole ratio of the compound having thestructure: ##STR79## to the compound having the structure: ##STR80##being 65:35. (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 5 is the NMR spectrum of the mixture of compounds having thestructures: ##STR81## subsequent to re-purification (Conditions: Fieldstrength: 100 MHz; Solvent: CFCl₃).

FIG. 6 is the NMR spectrum for the compound having the structure:##STR82## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE IV PREPARATION OF 2,6-DIMETHYL-7,7-BIS(METHYLTHIO)-2-HEPTENE

Reaction: ##STR83##

Into a 500 cc reaction flask equipped with stirrer, thermometer, refluxcondenser, cooling bath and gas bubbler is placed 200 ml of methylenedichloride (CH₂ Cl₂); 0.5 grams paratoluene sulfonic acid and 23.0 gramsof melonal having the structure: ##STR84## The reaction mass is cooledto 0° C. using the ice-isopropyl alcohol cooling bath. With stirringover a period of 12 hours, 25 grams of methyl mercaptan is bubbled intothe reaction flask. The reaction mixture is stirred at 0° C. for another3 hours. At the end of this period, the reaction mass is washed with 3volumes of aqueous saturated sodium chloride followed by 3 volumes of 10percent sodium bicarbonate solution. The solvent is stripped off and thereaction mass is then fractionally distilled yielding the compoundhaving the structure: ##STR85## in 99 percent pure form. This compoundhas an excellent hydrolyzed vegetable protein-like, beany and cookedvegetable aroma and taste profile at 0.01 ppm causing it to be useful inhydrolyzed vegetable protein and cooked bean flavored foodstuffs.

FIG. 7 is the NMR spectrum for the compound having the structure:##STR86## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE V TRUE FRUIT FLAVOR

The following "true fruit flavor" formulation is prepared:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        Heliotropine       10.0                                                       Benzaldehyde       5.0                                                        Paratoluacetaldehyde                                                                             3.2                                                        Vanillin           2.0                                                        Ethyl-3-methyl-3-phenyl                                                                          4.0                                                        glycidate                                                                     Phenylethylacetaldehyde                                                                          2.1                                                        Benzylacetate      2.3                                                        Maltol             2.0                                                        Benzylalcohol      6.2                                                        Ethyl maltol       2.4                                                        Cis-2-methyl-2-pentenoic acid                                                                    3.4                                                        3,4-pentadienoic acid, ethyl                                                                     4.1                                                        ester                                                                         The compound having                                                                              2.8                                                        the structure:                                                                 ##STR87##                                                                    prepared according                                                            to Example I, supra.                                                          Propylene glycol   70.0                                                       ______________________________________                                    

The resulting true fruit flavor is compared in water at the rate of 20ppm with and without the addition of the compound having the structure:##STR88## prepared according to Example I. The flavor with the compoundhaving the structure: ##STR89## has an excellent, natural, blueberry,blackcurrant character in both aroma and taste. Therefore, it ispreferred by a bench panel consisting of five members as being morenatural and more characteristic of natural fruit.

EXAMPLE VI

A. POWDER FLAVOR FORMULATION

20 Grams of the flavor composition of Example V is emulsified in asolution containing 300 gm gum acacia and 700 gm water. The emulsion isspray-dried with a Bown Lab Model Drier utilizing 260 c.f.m. of air withan inlet temperature of 200 F. and a wheel speed of 50,000 rpm.

B. SUSTAINED RELEASE FLAVOR

The following mixture is prepared:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Liquid True Fruit 20.00                                                       Flavor Composition                                                            of Example V                                                                  Propylene glycol  9.00                                                        Cab-O-Sil         5.00                                                        (Brand of Silica                                                              produced by the                                                               Cabot Corporation of                                                          125 High Street,                                                              Boston, Mass. 02110;                                                          Physical Properties:                                                          Surface Area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft.                                                       ______________________________________                                    

Cab-O-Sil is dispersed in the liquid true fruit flavor composition ofExample V with vigorous stirring, thereby resulting in a viscous liquid.71 Parts by weight of the powder flavor composition of Part A, supra, isthen blended into the said viscous liquid, with stirring, at 25° C. fora period of 30 minutes resulting in a dry, free flowing sustainedrelease flavor powder.

EXAMPLE VII

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of Example Vis added to the solution which is then homogenized to form an emulsionhaving particle size typically in the range of 2-5 microns. Thismaterial is kept at 120° F. under which conditions the gelatin will notjell.

Coacervation is induced by adding slowly and uniformly 40 parts byweight of a 20 percent aqueous solution of sodium sulphate. Duringcoacervation the gelatin molecules are deposited uniformly about eachoil droplet as a nucleus.

Gelatin is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7 aqueous solution of sodium sulphate at 65° F. Theresulting jelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37 percent solution of formaldehyde inwater. The cake is then washed to remove residual formaldehyde.

EXAMPLE VIII CHEWING GUM

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example VI(B). Mixing is effected ina ribbon blender with jacketed side walls of the type manufactured bythe Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long-lastingtrue fruit flavor with excellent blueberry and blackcurrant nuances.

EXAMPLE IX CHEWING GUM

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example VII. 300 Parts of sucrose and100 parts of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long-lasting"true fruit" flavor with intense blackberry and blackcurrant aroma andtaste nuances.

EXAMPLE X TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight        Ingredients                                            ______________________________________                                        Group "A"                                                                     30.200                 Glycerine                                              5.325                  Distilled water                                        .100                   Sodium Benzoate                                        .125                   Saccharin Sodium                                       .400                   Stannous Fluoride                                      Group "B"                                                                     12.500                 Calcium Carbonate                                      37.200                 Dicalcium Phosphate                                                           (Dihydrate)                                            Group "C"                                                                     2.000                  Sodium N--Lauroyl                                                             Sarcosinate (foaming                                                          agent)                                                 Group "D"                                                                     1.200                  Flavor material of                                                            Example VI(B)                                          111.00     Total                                                              ______________________________________                                    

PROCEDURE:

1. The ingredients in Group "A" are stirred and heated in a streamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly thesodium-n-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to three roller mill and the homogenized, andfinally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant "true fruit" flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XI CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example VI(B)is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich Chewable Vitamin Tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                           Gms/1000 Tablets                                           ______________________________________                                        Vitamin C (absorbic acid) as                                                                       70.11                                                    ascorbic acid-sodium ascorbate                                                mixture 1:1                                                                   Vitamin B.sub.1 (thiamine mononitrate)                                                             4.0                                                      as Rocoat ® thiamine mononi-                                              trate) as Rocoat ®                                                        thiamine mononitrate                                                          331/3% (Hoffman La Roche)                                                     Vitamin B.sup.2      5.0                                                      (riboflavin) as                                                               Rocoat ®                                                                  riboflavin 331/3%                                                             Vitamin B.sub.6 (pyridoxine                                                                        4.0                                                      hydrochloride)                                                                as Rocoat ®                                                               pyridoxine hydro-                                                             chloride                                                                      331/3%                                                                        Niacinamide as Rocoat ®                                                                        3.0                                                      niacinamide                                                                   331/3%                                                                        Calcium pantothenate 11.5                                                     Vitamin B.sub.12 (cyanocobalamin) as                                                               3.5                                                      Merck 0.1% in gelatin                                                         Vitamin E (dl-alpha- 6.6                                                      tocopheryl                                                                    acetate) as dry                                                               Vitamin E acetate                                                             331/3%                                                                        d-Biotin              0.044                                                   Flavor of            (as indicated above)                                     Example IV(B)                                                                 Certified lake color 5.0                                                      Sweetener - sodium   1.0                                                      saccharin                                                                     Magnesium stearate   10.0                                                     lubricant                                                                     Mannitol q.s. to make                                                                              500.0                                                    ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A Acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 gm each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong "true fruit" flavor for a period of 12 minutes.

EXAMPLE XII

At the rate of 3 ppm the compound having the structure: ##STR90##prepared according to Example I placed in a 95% foodgrade ethanolsolution at the rate of 10% is added to CARMEL KOSHER® vegetable gel (85gram package) having the following contents:

Sugar

Carrageenan

Citric acid

Potassium citrate ##STR91## The resulting product is added to 16 ouncesof boiling water and stirred for a period of 1.5 minutes. The resultingmaterial is poured into a mold and is permitted to cool. The resultingjell has an excellent "true fruit" flavor with intense blueberry andblackcurrant nuances. Note: CARMEL KOSHER® vegetable jell is produced byCarmel Kosher Food Products, Inc. of Chicago, Ill. 60632.

EXAMPLE XIII GUAVA NECTAR

At the rate of 0.2 ppm, the mixture of compounds having the structures:##STR92## produced according to Example II(A)(ratio of compound havingthe structure: ##STR93## to the compound having the structure: ##STR94##being 80:20) is added to GOYA® GUAVA NECTAR produced by Goya ProductsInc. The resulting guava nectar has a more natural-like taste and theguava nectar not containing the mixture of compounds having thestructures: ##STR95## The resulting guava nectar also has a faint,pleasant, aesthetically pleasing grapefruit nuance.

EXAMPLE XIV

Three meat loaf type products are prepared according to the followingformulation:

    ______________________________________                                        Ingredients             Amount                                                ______________________________________                                        TVP, minced             1     cup                                             Ground beef             1     cup                                             Water                   1     cup                                             Beef suet               1/3   cup                                             Bread crums, dry, unflavored                                                                          1     cup                                             Whole milk              1     cup                                             Egg albumen             3     tbsp.                                           Salt                    11/4  tbsp.                                           Black pepper            1/4   teasp.                                          Catsup                  1/4   cup                                             Water                   32    ml.                                             ______________________________________                                    

1 "TVP" is a texturized vegetable protein mixture made byArcher-Daniels-Midland Company.

Three separate portions prepared according to the foregoing formulationare made into three meat loaves. Loaf A contains no additional additive.Loaf B contains 32 ml of fresh pressed onion juice to replace the 32 mlof water. Loaf C contains 5 ppm of the mixture prepared according toExample III containing the compounds having the structures: ##STR96##with the ratio of compound having the structure: ##STR97## with theratio of compound having the structure: ##STR98## to the compound havingthe structure: ##STR99## being 65:30. The three loaves are baked at 350°F. for 1 hour.

The Loaves B and C are judged superior to Loaf A because of the onioncharacter of B and the onion/garlic character of C enhances the overalltaste and covers the dry, cardboard-like cereal character of Loaf A.

EXAMPLE XV

The compound having the structure: ##STR100## prepared according toExample IV, supra is added to a 2% solution of Wyler's "Beef FlavorInstant Bouillon" (manufactured by Wyler Foods, Division of Borden,Inc., Chicago, Ill., United States).

Ingredients

salt

hydrolyzed vegetable protein

malto dextrin

sugar beef fat

water

monosodium glutamate

flavorings

corn sugar

beef extract

caramel

color

hydrogenated vegetable fat; and

U.S. certified food color

at the rate of 0.1 ppm. The resulting beef flavor has a beany, cookedvegetable, hydrolyzed vegetable protein, sweet and meaty aroma and tasteprofile. The hydrolyzed vegetable protein nuance are more natural-likeand more intense than the beef gravy not containing the compound havingthe structure: ##STR101##

A meat gravy is prepared containing 0.2 ppm by weight of the compoundhaving the structure: ##STR102## prepared according to Example IV usinga beef base and beef fat. The resulting beef gravy containing thecompound having the structure: ##STR103## is then added to mushroomscooked using boiling water at a rate of 10 parts gravy to 100 partscooked mushroom. The resulting mushroom platter has an excellentnatural-like beefy, savoury mushroom flavor with bready and savouryhydrolyzed vegetable protein nuances.

EXAMPLE XVI PREPARATION OF 2,6,6-TRIMETHYL-1-CYCLOHEXENE-1-ACID ALDEHYDEDIETHYL MERCAPTAL AND2-[-2-(ETHYLTHIO)ETHENYL]-1,3,3-TRIMETHYL-CYCLOHEXENE

Reaction ##STR104##

Into a Parr bomb is placed 16.6 grams beta-homocylcocitral having thestructure: ##STR105## 12 grams ethyl mercaptan; 40 ml methyl dichlorideand 0.1 grams paratoluene sulfonic acid. The Parr bomb is closed andwith stirring, the contents of the Parr bomb is heated to 100° C. TheParr bomb is shaken at 100° C. for a period of 5 hours. At the end ofthe 5 hour period, the Parr bomb is opened and the contents are washedwith two volumes of 10% aqueous sodium carbonate followed by one volumeof 50 ml of water. The resulting reaction mass is dried over anhydroussodium sulfate and the methylene dichloride is evaporated on a Buchievaporator. The resulting reaction mass is then distilled on a microdistillation column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         105/94       /148    6                                              2          97          162     6                                              3         130          172     6                                              4         143          175     6                                              5         160          180     6                                              6         160          180     6                                              7         155          220     6                                              ______________________________________                                    

The resulting product contains two compounds; the compound having thestructure: ##STR106## and the compound having the structure: ##STR107##

FIG. 8 is the GLC profile for the crude reaction product (Conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute). Thepeak indicated by reference numeral 81 is the peak for the compoundhaving the structure: ##STR108##

The peak indicated by reference numeral 82 is the peak for the compoundhaving the structure: ##STR109## The compound having the structure:##STR110## has a garlic and fried onion aroma and taste profile at 20ppm causing it to be useful in onion soup flavored foodstuffs and garlicflavored foodstuffs. The compound having the structure: ##STR111## has afloral, green and roasted aroma and taste profile at 0.5 ppm causing itto be useful in almond, roasted peanut and baked goods flavoredfoodstuffs.

FIG. 9 is the NMR spectrum for the compound having the structure:##STR112## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 10 is the NMR spectrum for the peak indicated by reference numeral82 for the compound having the structure: ##STR113## (Conditions: Fieldstrength: 100 MHz; Solvent: CFCl₃).

EXAMPLE XVII PREPARATION OF 2,6,6,6-TRIMETHYL-1-CYCLOHEXENE-1-ACIDALDEHYDE DIPROPYL MERCAPTAL AND1,3,3-TRIMETHYL-2[2-(PROPYLTHIO)ETHENYL]CYCLOHEXENE

Reaction: ##STR114##

Into a Parr bomb equipped with stirrer is placed 10 grams ofbeta-homocyclocitral having the structure: ##STR115## 13.8 grams propylmercaptan; 50 ml methylene dichloride and 0.1 grams of paratoluenesulfonic acid. The Parr bomb is sealed and heated with stirring to 110°C. The reaction mass is continued to be heated at 110° C. for a periodof 7 hours. At the end of the 7 hour period, the Parr bomb contents arecooled and the Parr bomb is opened. The contents are washed with 2volumes of 10% sodium carbonate solution followed by one 50 ml portionof water. The reaction mass is then dried over anhydrous sodium sulfateand the solvent is removed therefrom using a Buchi evaportor. Thereaction mass is then distilled on a micro distillation column yieldingthe following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         /107          70     6                                              2         109          180     7                                              3          75          194     6                                              4         119          200     8                                              5         --           205     8                                              ______________________________________                                    

The resulting product is a mixture of two compounds having thestructures: ##STR116##

The compound having the structure: ##STR117## is separated from thecompound having the structure: ##STR118## by means of preparative vaporphase chromatography. Fraction 2 contains primarily of a compound havingthe structure: ##STR119## Fraction 5 is primarily the compound havingthe structure: ##STR120##

FIG. 11 is the GLC profile for the crude reaction product prior todistillation containing the compounds having the structures: ##STR121##The peak indicated by reference numeral 111 is the peak for the compoundhaving the structure: ##STR122## The peak indicated by reference numeral112 is the peak for the compound having the structure: ##STR123## (GLCConditions: Carbowax column programmed at 220° C. isothermal).

FIG. 12 is the NMR spectrum for the compound having the structure:##STR124## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 13 is the NMR spectrum for the compound having the structure:##STR125## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

The compound having the structure: ##STR126## has a sweet, cherry,marachino cherry, oniony and bacon aroma and taste profile at 0.1 ppmcausing it to be useful in cherry and black cherry foodstuffs. Thecompound having the structure: ##STR127## has an excellent onion,roasted, crisp roasted and bacon aroma and taste profile at 2 ppmcausing it to be useful in bacon, roasted nut, roasted onion, almond andpeanut flavored foodstuffs.

EXAMPLE XVIII(A) PREPARATION OF ONION FLAVOR MATERIAL

A mixture of 0.1 grams of the compound having the structure: ##STR128##is admixed with 0.1 grams of methyl 1-propanethiosulfinate; 0.6 grams ofpropyl 1-propanethiosulfinate, and 0.3 grams of allyl1-propanethiosulfinate. The resulting product is heated in a sealedvessel at 150° C. for 30 seconds. The thiosulfinates are partiallyconverted to sulfides.

The resulting mixture has a very strong, freshly cooked onion aromacharacter with garlic and fried onion nuances.

EXAMPLE XVIII(B)

A half gram of the mixture of Example XVIII(A) is emulsified in asolution containing the following materials:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Gum arabic        100.0                                                       Water             300.0                                                       Butylated hydroxy anisol                                                                         0.5                                                        (20% solution and ethanol)                                                    ______________________________________                                    

The resulting emulsion is spray dried in a Bowen Lab Model spray drierwith the inlet temperature of 500° F. and outlet temperature of 200° F.12 Grams of spray-dried material is mixed with 29.2 grams of thefollowing soup base:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Fine ground sodium chloride                                                                       35.62                                                     Hydrolyzed vegetable protein                                                                      27.40                                                     (Nestle 4 BE)                                                                 Monosodium glutamate                                                                              17.81                                                     Sucrose             10.96                                                     Beef fat             5.48                                                     Sethness caramel color                                                                              2.73.                                                   (powder B & C)                                                                ______________________________________                                    

The resulting mixture is then added to 12 ounces of boiling water and anexcellent onion flavored soup with interesting, garlic and fried onionnuances is obtained. When the compound having the structure: ##STR129##is replaced by the compound having the structure: ##STR130## interestingonion, roasted, crisp-roasted and faint bacon nuances are obtained atone tenth of the level of use of the compound having the structure:##STR131##

EXAMPLE XIX

A white bread dough mix is prepared by mixing 1350 gm wheat flour and800 ml water. To the mix is added:

    ______________________________________                                        Ingredients         Amount                                                    ______________________________________                                        Yeast               27.00                                                     NaCl                67.5                                                      Sucrose             54.00                                                     Shortening          40.5                                                      Non-fat dry milk powder                                                       Yeast food (Arkadv)  0.50                                                     manufactured by Fleisch-                                                      mann, Div. of Standard                                                        Brands                                                                        Softening agent     3.4                                                       (succinylated mono-                                                           glycerides) manufactured                                                      by Kraft Div. of                                                              National Dairy Products                                                       Corporation                                                                   ______________________________________                                    

Six grams of the compound having the structure: ##STR132## preparedaccording to Example XVII are added to the dough. The dough is thenmixed for 8 minutes and allowed to rise for 45 minutes at 40° C.

The dough is then baked for 45 minutes at 210° C. The bread stuffproduct obtained has a flavor note reminiscent of the crust of home madeGeorgian bread with almond, roasted and peanut nuances and hasacceptable and persistent flavor properties for a period of one week,and has good flavor characteristic when spread with margerine.

EXAMPLE XX

The compound having the structure: ##STR133## is added at the rate of0.1 ppm to a standard marachino cherry flavor. The resulting marachinocherry flavor is added to blanched cherries at the rate of 5%. Theresulting cherries have an excellent marachino cherry flavor with sweet,natural cherry nuances.

EXAMPLE XXI PREPARATION OF DIMETHYL MERCAPTAL OF BETA-HOMOCYCLOCITRAL

Reaction: ##STR134##

Into a 200 cc reaction vessel equipped with stirrer, thermometer, refluxcondenser and cooling bath and gas addition tube are placed 16.4 gramsbeta-homocyclocitral having the structure: ##STR135## 250 ml methylenedichloride; and 0.1 grams of paratoluene sulfonic acid.

Using a dry ice bath, the reaction mass is cooled with stirring to0°-10° C. Over a period of 8 hours, 10 grams of methyl mercaptan isadded through the addition funnel to the reaction flask. The reactionmass is then placed in a Parr bomb and sealed. The Parr bomb is heatedwith stirring to 110° C. and maintained at that temperature for a periodof 8 hours. At the end of the 8 hour period, the Parr bomb is cooled andopened and the reaction mass is transferred to a separatory funnel andwashed with two 50 ml portion of 10% sodium carbonate solution followedby one 50 ml portion of water. The reaction mass is then dried anddistilled on a micro distillation apparatus, first recovery the solventand then yielding the following fractions:

FIG. 14 is the GLC profile for the crude reaction product containing thecompounds having the structures: ##STR136## The peak indicated byreference numeral 140 is the peak for the methylene chloride. The peakindicated by reference numeral 141 is the peak for thebeta-homocyclocitral having the structure: ##STR137## The peak indicatedby reference numeral 142 is the peak for the compound having thestructure: ##STR138## The peak indicated by reference numeral 143 is thepeak for the compound having the structure: ##STR139## (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 15 is the GLC profile for Fraction 5 of the foregoing distillation.The peak indicated by reference numeral 150 is the peak for the compoundhaving the structure: ##STR140## (Conditions: 8'×0.125" SE-30 columnprogrammed at 100°-220° C. at 8° C. per minute).

FIG. 16 is the NMR spectrum for Fraction 5 of the foregoing distillationcontaining the compound having the structure: ##STR141## (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 17 is the NMR spectrum of a purified version of Fraction 5 of theforegoing distillation containing the compound having the structure:##STR142## "Z":"E" ratio=2:1.

The compound having the structure: ##STR143## "Z":"E" ratio=2:1.

EXAMPLE XXII

The following peach flavor is prepared:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Gamma-n-pentyl     3.0                                                        The compound having                                                                              6.0                                                        the structure:                                                                 ##STR144##                                                                   prepared according                                                            to Example XXI,                                                               distillation                                                                  Fraction 5, 85%                                                               purity: "Z":"E" ratio = 2:1.                                                  Amyl acetate       15.0                                                       Amyl butyrate      3.4                                                        Amyl formate       6.8                                                        Amyl vallirate     6.7                                                        Benzaldehyde       4.2                                                        Benzylacetate      2.1                                                        Bitter almond essence                                                                            4.8                                                        Cinnamon           0.1                                                        Ethyl acetate      2.2                                                        Ethyl capronate    18.4                                                       Gamma-undecalactone                                                                              18.4                                                       Ethyl valorate     7.3                                                        Orange, sweet,     4.8                                                        essential oil                                                                 Rum ether          2.2                                                        Vanillan           17.3                                                       Mandarin essential oil                                                                           21.4                                                       Propylene glycol   q.s.                                                       Vanillan           17.3                                                       Mandarin essential oil                                                                           21.4                                                       Propylene glycol   q.s.                                                       ______________________________________                                    

The resulting flavor is added at the rate of 100 ppm to GOYA® NECTARDEGUANABANA. The resulting Guanabana nectar has an excellent naturalpeach undertone causing it to be more aesthetically pleasing to a benchpanel of five members (blind panel; not associated with inventive entityor assignee of instant application) over the same Guanabana nectarwithout the flavor or with the flavor, not containing the compoundhaving the structure: ##STR145##

What is claimed is:
 1. A process for augmenting or enhancing the aromaor taste of a foodstuff comprising the step of intimately admixing withsaid foodstuff from about 0.001 ppm up to about 250 ppm of a compounddefined according to the structure:wherein R₃ represents C₁ -C₃ alkyl.2. The process of claim 1 wherein R₃ is n-propyl.
 3. The process ofclaim 1 wherein R₃ is methyl.
 4. The process of claim 1 wherein R₃ isethyl.